High density brines (completion brines) have been widely used in well completion and workover operations in oilfields in the past several decades. The completion brines are salt solutions typically having fluid densities ranging from about 8.4 ppg (pounds per gallon) to about 20 ppg. Depending on the density desired, a completion brine can be a one salt solution (e.g. NaCl, NaBr, CaCl2, CaBr2, ZnBr2 or formate salt in water), a two salt solution (e.g. CaCl2/CaBr2 or ZnBr2/CaBr2), or a three salt solution (e.g. ZnBr2/CaBr2/CaCl2). The composition of the brines determines the fluid properties such as pH, density, etc. Depending on the economics, a fluid can be used in a well and then purchased back to be cleaned and reused later.
At the conclusion of any completion or workover project, a substantial volume of “contaminated” or unneeded completion/workover fluid typically remains. Such fluids may be contaminated with any or all of the following: water, drilling mud, formation materials, rust, scale, pipe dope, and viscosifiers and bridging agents used for fluid-loss-control pills. Depending on their composition and level of contamination, these fluids may or may not have further practical or economic value. If it is deemed that the fluids have future use potential, they may be reclaimed. Conversely, if they are determined to have no further use, they must be disposed of in an environmentally responsible way.
The benefits derived from the use of solids-free fluids, and especially high-density brines, for completion and workover operations have been extensively documented in the literature. Unfortunately, the costs associated with the initial purchase and subsequent disposal of such brines has been a hindrance to their universal acceptance especially since the “use once and dispose” means of disposal is neither prudent nor economically sound.
Because of the relatively high cost and limited worldwide natural mineral resources available for producing medium- and high-density completion/workover fluids, it is essential that their used fluids be reclaimed. The reconditioned fluids must meet the same specifications as those of “new” or “clean” fluids. With respect to completion/workover fluids, the term “clean” denotes not only the absence of suspended solids but also the absence of undesirable colloidal or soluble species which are capable of undergoing adverse reactions with formation, formation fluids or other completion fluids to produce formation-damaging insoluble substances.
There are many known methods for removing contaminates from a brine solution. One approach is to remove suspended solids by filtration. Simple filtration processes, wherein the brine is filtered through a plate and frame type filter press with the use of a filter aid such as diatomaceous earth and then through a cartridge polishing filter, are effective to remove solid contamination but they have no effect on removing other types of contamination such as colloidal or soluble species. This is the case since colloidally dispersed and soluble contaminants cannot be removed by filtration without first treating the fluid to change the chemical and/or physical properties of the contaminants. The treatments required to salvage the fluid depend on the nature of the contaminants incorporated and their chemical and physical properties.
A common contaminant in completion fluids is created by iron. In most non-zinc containing brines, it is relatively easy to treat for iron though careful attention must be made by the analyst. Zinc containing high-density brines have proven to be the most difficult to treat for iron removal. Most of the zinc based brines have relatively low pH which often leads to high iron contamination during use as completion and/or workover fluids. Iron contamination in such fluids can reach several hundred or even thousand milligrams per liter. Further, iron in zinc brine solutions is more likely to be in a soluble and stable form. Because of the low solubility of oxygen in such solutions, a significant percentage of the iron contaminants exists as ferrous iron. As a result, precipitation of iron hydroxide with the addition of calcium hydroxide, calcium oxide, or other basic material is difficult to achieve because the brine is highly buffered through aqueous zinc hydroxide complexes, which makes it nearly impossible to raise the pH appreciably. Additionally the pH of these zinc-containing fluids cannot be adjusted above about 6.0. Nonetheless, adding lime or other basic (suspended) material to adjust brine pH can be an important step in the reclamation process which often consists of multiple steps, including filtration, pH adjustments, oxidation, etc.
One brine reclamation process of the prior art consists of the oxidation of polymeric species to reduce the viscosity and yield point of the contaminated brine, oxidation of Fe++ to Fe+++ to facilitate removal of iron, and the oxidation of organic species which interfere with the reclamation process.
Another brine reclamation process of the prior art consists of the initial filtration of the brine followed by a reduction in the pH of the brine fluid. Carbon or bentonite absorbent is then added to the brine and the solution is allowed to stand for about six hours. The resulting solids are then filtered and the pH of the resulting system is slowly raised. The fluid is then re-filtered and tested for compatibility. Yet another multi-step reclamation process is disclosed in U.S. Patent Pub. No. 2002/0130090. In this process, the spent brine is mixed with acid in order to lower the pH. The fluid is then contacted with a halogen, such as bromine, to increase the density. A reducing agent, such as anhydrous ammonia, is then added. An alkali is then used to neutralize any excess acid. Finally any suspended solid impurities are removed.
Such multi-step processes for reclaiming brine solutions are flawed. First, such processes often take very long to complete which, in turn, increases expenses as more man-hours and more hours of equipment usage are required to complete the reclamation. They are also expensive because they require the addition of multiple chemical agents. In many cases, pH adjustments lead to a reduction in the brine density and a reduction in the resale value of the brine. Further, QA/QC is difficult to control in light of the multi-steps involved.
Therefore there exists a need for an improved method of reclaiming spent brine fluid. There is a need for a process that works independent of property changes to the system, such as pH and temperature. In addition, an improved process is needed which is easier to control in QA/QC.